Color photographic light-sensitive material containing UV filter compounds

ABSTRACT

A color photographic light-sensitive material comprising a reflective support having thereon a plurality of silver halide emulsion layers of which the emulsion layer located farthest from said support has, on each of both the support side thereof and the uppermost side at least one nonlight-sensitive layer containing an effective amount of an ultraviolet absorbing agent, said ultraviolet absorbing agent being used in said nonlight-sensitive layer on the uppermost side of said emulsion layer being a 2-(2&#39;-hydroxyphenyl)benzotriazole-type compound which is in the liquid form at normal room temperature.

This application is a continuation of application Ser. No. 055,726,filed May 21, 1987, now abandoned, which is a Reissue Application ofSer. No. 500,963, filed Jun. 3, 1983 and issued as U.S. Pat. No.4,518,686.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates particularly to a color photographiclight-sensitive material for use in making photographic prints.

2. Prior Art and the Problems Thereof

Conventionally color photographic light-sensitive materials for use inmaking photographic prints are generally formed by coating in order on areflective support an yellow coupler-containing blue-sensitive silverhalide emulsion layer, nonlight-sensitive first interlayer, magentacoupler-containing green-sensitive silver halide emulsion layer,nonlight-sensitive second interlayer, cyan coupler-containingred-sensitive silver halide emulsion layer and nonlight-sensitiveprotective layer.

And particularly in order to prevent the discoloration by ultravioletrays of the dyes formed by a color development from the respectivecouplers, an ultraviolet absorbing agent is added to the secondinterlayer.

However, such conventional print-making color photographiclight-sensitive materials have a disadvantage that the dyes formed by acolor development from the respective couplers used, particularly themagenta dye and the cyan dye are poor in the resistance to light, tendsto be discolored by light with time, and become out of color balanceafter being discolored.

In that case, if the protective layer also contains an ultravioletabsorbing agent, the resistance to light could be improved.

And by doing so, there is no doubt that the resistance to light of thelight-sensitive material can be improved. However, there still existsanother disadvantage that the light-sensitive material, after beingprocessed, loses as time goes by the gloss on the surface thereof bylight, heat, moisture, and the like; i.e., the so-called sweatphenomenon arises, thus deteriorating the image quality.

OBJECT OF THE INVENTION

The present invention has been made in view of such a situation asdescribed above, and the principal object of the present invention is toprovide a color photographic light-sensitive material which is improvedso as to prevent possible deterioration of the gloss on the surfacethereof caused with time by light, heat, moisture, and the like, andcapable of forming a highly light-resistant dye image.

As a result of our various studies on this problem, it has now beenfound that the above object of the present invention is accomplished byincorporating a 2-(2′-hydroxyphenyl)benzotriazole-type compound in theliquid form at normal room temperature into the overcoat layer on theuppermost silver halide emulsion layer of a multilayered colorphotographic light-sensitive material.

Namely, the present invention is of a color photographic light-sensitivematerial comprising a reflective support having thereon a plurality ofsilver halide emulsion layers, of which the emulsion layer locatedfarthest from the support has, on each of both the support side thereofand the opposite side thereof to the support side, at least onenonlight-sensitive layer containing an ultraviolet absorbing agent, saidultraviolet absorbing agent used in said nonlight-sensitive layer onsaid opposite side of said emulsion layer against said support being a2-(2′-hydroxyphenyl)benzotriazole-type compound which is in the liquidform at normal room temperature.

EMBODIMENT OF THE INVENTION

The embodiment of the present invention will be illustrated in detailbelow:

The color photographic light-sensitive material of the present invention(hereinafter referred as to the light-sensitive material) has not lessthan two silver halide emulsion layers, and, in the normal form, hasthree spectrally different light-sensitive silver halide emulsion layerseach differently having one of three nondiffusible yellow, magenta andcyan couplers.

The combination of the light-sensitive silver halide emulsion layerswith the couplers in a normal instance is such that the cyan coupler isin the red-sensitive silver halide emulsion layer, the magenta couplerin the green-sensitive silver halide emulsion layer, and the yellowcoupler in the blue-sensitive silver halide emulsion layer.

There are no special restrictions on the coating order of suchrespective emulsion layers.

Usually, however, from the reflective support side the yellowcoupler-containing emulsion layer, magenta coupler-containing emulsionlayer and cyan coupler-containing emulsion layer are coated in thedescribed order. Alternatively, if desired, these layers may also becoated in such an order as of the cyan coupler-containing emulsionlayer, magenta coupler-containing emulsion layer and then yellowcoupler-containing emulsion layer.

As the yellow, magenta and cyan couplers to be used in the presentinvention, any known couplers may be used.

Preferred yellow couplers include α-pivaloylacetanilide-type couplers.

Preferred magenta, couplers include 5-pyrazolone-type, more preferably,1-phenyl-5-pyrazolone-type, and further preferably1-phenyl-3-anilino-5-pyrazolone-type couplers and pyrazolotriazole-typecouplers.

Preferred cyan couplers include phenol-type couplers.

Any of these couplers may be contained in an amount of from 0.05 to 1mole per mole of silver halide in any of the above silver halideemulsion layers.

Of these silver halide emulsion layers, the silver halide emulsion layerlocated farthest from the support is provided on each of both thesupport side thereof and the opposite side thereof to the support sidewith a nonlight-sensitive layer.

These nonlight-sensitive layers comprise such a hydrophilic binder as,e.g., gelatin.

And the nonlight-sensitive layers each contains an ultraviolet absorbingagent.

In this instance, the binder coating amount in each of thenonlight-sensitive layers is normally from 1 to 30 mg/dm².

On the other hand, of these nonlight-sensitive layers, the one locatedfarther from the support on the emulsion layer located farthest from thesupport contains not less than one of2-(2′-hydroxyphenyl)benzotriazole-type compounds which are in the liquidform at normal room temperature. These2-(2′-hydroxyphenyl)benzotriazole-type compounds preferably have themelting point of not more than 30° C., more preferably not more than 15°C.

The compounds herein are required to be in the liquid form, and, if not,they cannot display the effect to improve the so-called sweatphenomenon, and even if in the liquid form, any ultraviolet absorbingagents other than 2-(2′-hydroxyphenyl)benzotriazole-type compoundscannot carry out the improvement on the prevention of the sweatphenomenon.

The 2-(2′-hydroxyphenyl)benzotriazole-type compounds preferably have theformula:

wherein R₁ and R₂ represent an alkyl, an aryl, an alkoxy and aryloxyradical, and R₃ represents a hydrogen atom, a halogen atom, an alkyl, anaryl, an alkoxy, an aryloxy, an alkenyl, a nitro or a hydroxyl radical.

More preferably, the compounds having the formula [I] is represented byFormula [II], [III], [IV] or [V]:

wherein R₄ represents a methyl, ethyl or propyl radical, R₅ represents asecondary alkyl having from 4 to 10 carbon atoms, R₆ represents ahydrogen atom, a halogen atom, an alkyl, or an alkoxy radical havingfrom 1 to 8 carbon atoms;

wherein R₇, R₈ and R₉ independently represent an alkyl radical havingfrom 4 to 10 carbon atoms, provided that at least one of R₇, R₈ and R₉represents a secondary alkyl;

wherein R₁₀ represents a secondary or tertiary alkyl from 1 3to 8 carbonatoms, X represents an alkylene from 1 to 6 carbon atoms, R₁₁ representsan alkyl group from 1 to 12 carbon atoms, R₁₂ represents the sameradical as defined by R₆;

wherein R₁₃ and R₁₄ independently represent a secondary alkyl havingfrom 4 to 10 carbon atoms and R₁₅ represents the same radical as definedby R₆.

The following are typical examples of those2-(2′-hydroxyphenyl)benzotriazole-type ultraviolet absorbing agentswhich are in the liquid form at normal room temperature, but are notlimited thereto.

Any of these liquid 2-(2′-hydroxyphenyl)benzotriazole-type ultravioletabsorbing agents may be incorporated singly or in combination of notless than two kinds into the nonlight-sensitive layer adjacent to theouter side (opposite from the support) of the silver halide emulsionlayer located farthest from the support.

Any of these liquid ultraviolet absorbing agents may be added to thenonlight-sensitive layer also in combination with any of otherultraviolet absorbing agents which are in the solid form at normal roomtemperature.

Those suitably available solid ultraviolet absorbing agents are2-(2′-hydroxyphenyl)benzotriazole-type ultraviolet absorbing agentswhich are in the solid form at normal room temperature, particularly at15° C. These compounds preferably have the melting point of not lessthan 15° C., more preferably not less than 30° C.

If the solid ultraviolet absorbing agent is used in combination with theliquid one, because the molecular weight of the solid one is generallysmaller than that of the liquid one, the adding amount by weight of theultraviolet agent can be reduced, or in the same adding amount, thelight-resistant effect of the resulting dye image can be improved.Further, such combined use is advantageous in respect that the usingamount of high-boiling solvents that will be described hereinafter canbe reduced.

Those solid 2-(2′-hydroxyphenyl)benzotriazole-type ultraviolet absorbingagents are of the foregoing formula but substituted at the 3′-, 5′- and5-positions each with hydrogen, a halogen, an alkyl, an aryl, an alkoxy,an aryloxy, an alkenyl, hydroxy, nitro or the like radical.

And if these 2-(2′-hydroxyphenyl)benzotriazole ultraviolet absorbingagents are used, the diffusion thereof in the added layer is small, andthe compatibility thereof with the liquid ultraviolet absorbing agentsis excellent, thus giving satisfactory results.

The following are typical examples of such liquid solid2-(2′-hydroxyphenyl)benzotriazole ultraviolet absorbing agents:

In addition, these liquid and solid benzotriazole-type compounds aredescribed in Japanese Patent Examined Publication Nos. 10466/1961,26187/1967, 5496/1973 and 41572/1973, and U.S. Pat. Nos. 3,754,919 and4,220,711, and the like.

In contrast, no special restrictions are put on the use of ultravioletabsorbing agents in the nonlight-sensitive layer adjacent to the supportside of the silver halide emulsion layer located farthest from thesupport, so that they can be various kinds.

However, it is desirable, also in this case, to use2-(2′-hydroxyphenyl)benzotriazole-type ultraviolet absorbing agentshaving the following Formula [II] because they have satisfactorycompatibility with high boiling solvents and are less-diffusible in thelayer:

wherein R₁, R₂ and R₃ each represents hydrogen, a halogen, an alkyl, anaryl, an alkoxy, an aryloxy, an alkenyl, nitro or hydroxyl radical.

The ultraviolet absorbing agents used in this case may be either liquidor solid, and may be used either singly or in arbitrary combination ofnot less than two kinds.

And typical examples of these agents are the foregoing compounds UV-1Lto UV-14L and the above UV-1S to UV-19S.

These ultraviolet absorbing agents thus to be contained in the twononlight-sensitive layers may be contained in the respective layers in atotal amount in a ratio of 0.001-2 parts by weight per part by weight ofthe binder.

In addition, the ratio of the total amount of the ultraviolet absorbingagents in the nonlight-sensitive layer on the support side of theuppermost emulsion layer to the total amount of the ultravioletabsorbing agents in the nonlight-sensitive layer on the opposite side ofthe same emulsion layer from the support is desirable to be normallyfrom 1:0.1 to 1:100.

Thus, in order to incorporate the ultraviolet absorbing agent into thenonlight-sensitive layer, the agent, if in the liquid form, may, ifnecessary, be dissolved into a low-boiling solvent, the solution isfinely dispersed using a surface active agent into such a hydrophilicbinder as an aqueous gelatin solution, and this resulting dispersedliquid is then added to an objective hydrophilic colloidal layer.

Alternatively, in the case where a solid ultraviolet absorbing agent isused or where a liquid and solid ultraviolet absorbing agent arecombinedly used, they may, if necessary, be dissolved into ahigh-boiling solvent whose boiling point is not less than 175° C., or,if necessary, into a mixture of the high-boiling solvent with alow-boiling solvent, the solution is then finely dispersed using asurface active agent into such a hydrophilic binder as an aqueousgelatin solution, and the resulting dispersed liquid is then added to anobjective hydrophilic colloidal layer.

The high-boiling solvent used herein includes organic acid amides,carbamates, esters, ketones, urea derivatives, and the like, among whichparticularly preferred are esters including phthalic acid esters such asdimethyl phthalate, diethyl phthalate, dipropyl phthalate, dibutylphthalate, di-n-octyl, phthalate, diiso-octyl phthalatedi-(2-ethyl-hexyl)phthalate, diamyl phthalate, dinonyl phthalate,diisodecyl phthalate, and the like; phosphoric acid esters such astricresyl phosphate, triphenyl phosphate, tri-(2-ethyl-hexyl)phosphate,triisononyl phosphate, and the like; sebacic acid esters such as dioctylsebacate, di-(2-ethyl-hexyl)sebacate, diisodecyl sebacate, and the like;esters of glycerol such as glycerol tripropionate, glycerol tributyrate,and the like; and in addition, adipic acid esters, glutaric acid esters,succinic acid esters, maleic acid esters, fumaric acid esters, citricacid esters, and the like. These may be used singly or in combination ofnot less than two kinds.

The low-boiling solvent used herein includes methyl acetate, ethylacetate, propyl acetate, butyl acetate, butyl propionate, cyclohexanol,cyclohexane, tetrahydrofuran, methyl alcohol, ethyl alcohol,acetonitrile, dimethyl formamide, dioxane, methyl-ethyl ketone,methylisobutyl ketone, diethylene glycol monoacetate, acetyl acetone,nitromethane, nitroethane, carbon tetrachloride, chloroform, and thelike, and these may be used singly or in combination of not less thantwo kinds.

Further, as the surface active agent used herein, there may be used suchanionic surface active agents as alkylbenzene sulfonate,alkylnaphthalene sulfonate, and the like, and/or such nonionic surfaceactive agents as sorbitansesquioleic acid esters, sorbitanmonolauricacid esters, and the like.

The proportion of the using amount of the high-boiling solvent to thatof the ultraviolet absorbing agent is normally not more than 5 parts byweight to 1 part by weight.

In addition, it is desirable to form a nonlight-sensitive layer as aprotective layer composed substantially of a binder alone over andadjacent to the opposite side of the uppermost nonlight-sensitive layerfrom the support.

The forming of the protective layer enables to further reduce thephenomenon of losing the surface gloss with time; i.e., the so-calledsweat phenomenon.

The coating amount of the binder of the protective layer is normallyfrom about 1 to about 30 mg/dm².

Besides, it is desirable to provide a nonlight-sensitive interlayerbetween the emulsion layer located closest to the support and theintermediate emulsion layer.

This interlayer also has a hydrophilic binder, of which the coatingamount is desirable to be from 1 to 30 mg/dm².

The foregoing two nonlight-sensitive layers and the above interlayermay, if necessary, contain such an anti-stain agent as dioctylhydroquinone, dibutyl hydroquinone, and the like, a whiteness toningagent, a coating aid, and the like.

And the above-mentioned interlayer may, if necessary, be allowed tocontain an ultraviolet absorbing agent as well.

On the premise that the above-described conditions are used, as thedispersion methods for dispersing couplers in the light-sensitivematerial of the present invention, there may be used various methodssuch as the so-called aqueous alkaline solution dispersion method, soliddispersion method, latex dispersion method, oil-in-water-typeemulsification dispersion method, and the like, from among which anyarbitrary method may be selected to be used according to the chemicalstructure of the coupler used.

Those particularly preferred methods for the present invention are thelatex dispersion method and the oil-in-water-type emulsificationdispersion method.

These methods are conventionally well-known, and the latex dispersionmethod and the effect thereof are described in Japanese PatentPublication Open to Public Inspection (hereinafter referred to asJapanese Patent O.P.I. Publication) Nos. 74538/1974, 59943/1976 and32552/1979, and Research Disclosure Vol. 148, No. 14850 pp. 77-79,August 1976.

Those latexes appropriately usable in the latex dispersion method arehomopolymers, copolymers and terpolymers of such monomers as e.g.,styrene, ethyl acrylate, n-butyl acrylate, n-butyl methacrylate,2-acetoacetoxyethyl methacrylate,2-(methacryloyloxy)ethyl-trimethyl-ammonium-methosulfate, sodium3-(methyacryloyloxy)propane-1-sulfonate, N-isopropyl-acrylamide,N-[2-(2-methyl-4-oxopentyl)]acrylamide,2-acrylamide-2-methylpropanesulfonic acid, and the like. As theoil-in-water-type emulsification dispersion method, the conventionallyknown method for dispersing hydrophobic additives such as couplers maybe used which is carried out in the manner that the foregoing coupler isdissolved into a high-boiling solvent such as, for example, N-n-butylacetanilide, diethyl lauramide, dibutyl phthalate, tricresyl phosphate,N-dodecylpyrolidone, or the like, and the solution is then finelydispersed into a hydrophilic colloid such as gelatin.

The silver halide for use in the silver halide emulsion layers of thelight-sensitive material of this invention includes those silver halidesarbitrarily usable in ordinary silver halide photographic emulsions suchas silver chloride, silver bromide, silver iodide, silver chlorobromide,silver iodobromide, silver chloroiodobromide, and the like.

These silver halide particles may be either coarse-grained offine-grained, the distribution of which may be either narrower or wider.

And these silver particles may be in the crystal form either normal ortwinned having an arbitrary proportion of the [100] face to the [111]face. Further, the crystal structure of these silver halide particlesmay be either homogenious from the internal to the external orheterogeniously stratified with the internal and the external. Thesesilver halide particles may be either of the type of forming a latentimage mainly on the surface thereof or of the type of forming a latentimage thereinside.

These silver halide particles may be prepared by any known methodspracticed by those skilled in the art.

The silver halide emulsion to be used in the respective emulsion layersof the light-sensitive material of this invention is desirable to befree of water-soluble salts, but may remain undesalted, and further maybe a mixture of not less than two separately prepared different silverhalide emulsions.

As the binder for the silver halide emulsion layers and for thenonlight-sensitive layers, those conventionally known may be used. Thosesuitably usable include gelatin and gelatin derivatives such as, e.g.,phenyl-carbamylated gelatin, acylated gelatin, phthalated gelatin, andthe like. These binder materials may, if necessary, be used in thecompatible mixture form of not less than two kinds.

The silver halide photographic emulsion comprising silver halideparticles dispersed into a binder solution may be sensitized by chemicalsensitizers. Those chemical sensitizers advantageously usable in thepresent invention are broadly classified into 4: noble-metallicsensitizers, sulfur sensitizers, selenium sensitizers, and reductionsensitizers.

Noble-metallic sensitizers include gold compounds and compounds ofruthenium, rhodium, palladium, iridium, platinum, and the like.

When using gold compound, ammonium thiocyanate or sodium thiocyanate maybe used in combination therewith.

Sulfur sensitizers include active gelatin and other sulfur compounds.

Selenium sensitizers include active and inert selenium compounds.

Reduction sensitizers include stannous salts, polyamines,bisalkylaminosulfide, silane compounds, iminoaminomethanesulfinic acid,hydrazinium salts and hydrazine derivatives.

The light-sensitive material of this invention may contain, in additionto the foregoing additives, a stabilizer, development accelerator,hardening agent, surfactant, antistain agent, lubricant, brighteningagent mordant, DIR compound, or various other photographically usefuladditives.

The light-sensitive material of this invention may be furtherarbitrarily provided with a backing layer in addition to the silverhalide emulsion layers, the foregoing nonlight-sensitive layers,interlayers and protective layer.

As the reflective support of the light-sensitive material of theinvention, those conventionally known materials such asplastic-laminated paper, baryta paper, synthetic paper, and the like,may be arbitrarily selected to be used according to uses. These supportmaterials are generally subjected to various treatments for increasingthe adherence thereof to the emulsion layer.

ACTION OF THE INVENTION

The light-sensitive material of this invention, after being exposed tolight through a negative material having an image composed of couplingproducts, is subjected to color development.

The color development is carried out by an ordinary color developingmethod.

Namely, the light-sensitive material is first processed in a colordeveloping bath containing a color developing agent. Otherwise, a colordeveloping agent or a precursor thereof is in advance incorporated intothe light-sensitive material, which is then processed in an activatorsolution. After that, in general, the material is bleached and thenfixed in the usual way.

The color development by use of a color developer bath or of anactivator bath, the bleaching, and the fixing may be independentlycarried out, but instead of carrying out such two or more processesindependently, it is also possible to conduct such processes at a timeby use of a processing solution having these functions (monobath); forexample, the processing in a monobath of a color developer or anactivator containing a bleaching agent and a fixing agent that will behereinafter described, or the color development followed by theprocessing in a bleach-fixing bath containing a bleaching agent andfixing agent, and the like.

Otherwise, although the color development by use of the color developerbath or of the activator bath may be immediately followed by thebleach-fixing bath processing for desilvering, an acid stop bathprocessing may be provided in between the color development and thebleach-fixing bath processing.

The acid stop bath may be an aqueous solution of acetic acid or citricacid. And, if necessary, such processing as prehardening, neutralizingthereof, washing, stabilization, and the like, may be further provided.

When the print-making light-sensitive material is subjected to theabove-described processings, a dye image is formed by the couplingreaction inside the light-sensitive material.

The color developing agent used in the processing of the light-sensitivematerial of this invention is typified by aromatic primary amine colordeveloping agents.

Aromatic primary amine color developing agents include aminophenol-typeand p-phenylenediamine-type derivatives. These compounds may be used inthe free form or in the form of the hydrochloride thereof, of thesulfate thereof, or of such organic acid salts thereof asp-toluenesulfonate, tetraphenylborate, p-(t-octyl)-benzenesulfonate, andthe like.

Typical examples of aromatic primary amine color developing agents areo-aminophenol, p-aminophenol, 5-amino-2-oxytoluene,2-amino-3-oxytoluene, 2-oxy-3-amino-1,4-dimethylbenzene,N,N-diethyl-p-phenylenediamine hydrochloride,N-methyl-p-phenylenediamine hydrochloride,N-N-dimethyl-p-phenylenediamine hydrochloride,N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline and thesulfate thereof, N-ethyl-N-β-hydroxyethylaminoaniline,N-N-diethyl-3-(β-methanesulfonamidoethyl)-4-aminoaniline hydrochloride,4-amino-N-(2-methoxyethyl)-N-ethyl-3-methylaniline-p-toluenesulfonate,N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoanilinetetraphenylborate, 4-amino-N-(2-methoxyethyl)-N-ethyl-3-methylaniline-tetraphenylborate, p-morpholinoaniline, p-piperidinoaniline,4-amino-N,N-diethyl-3-chloroaniline, and the like.

The light-sensitive material of this invention may, if necessary,contain a color developing agent precursor. The color developing agentprecursor is a compound capable of producing a color developing agentunder an alkaline condition, which includes, e.g., Schiff's base-typeprecursors with aromatic aldehyde derivatives, multivalent-metallic ioncomplex precursors, phthalic acid imide derivative precursors,phosphoric acid amide derivative precursors, sugar-amine reactantprecursors and urethane-type precursors.

These aromatic primary amine color developing agent precursors are asdescribed in, e.g., U.S. Pat. Nos. 3,342,599, 2,507,114, 2,695,234 and3,719,492, British Pat. No. 803,783, Japanese Patent O.P.I. PublicationNos. 135628/1978 and 79035/1979, and Research Disclosure Nos. 15159,12146 and 13924.

Any of these aromatic primary amine color developing agents arecontained in an amount of normally from 1 to 20 g/liter in the colordeveloping solution. If contained in the precursor form in thelight-sensitive material, the precursor is incorporated in an amount ofnormally from 0.5 to 3 moles per mole of silver halide.

The color developing solution or activator solution for use in thelight-sensitive material of this invention contains such an alkali agentas potassium hydroxide, sodium hydroxide, sodium carbonate, potassiumcarbonate, sodium tertiary phosphate, potassium tertiary phosphate, andthe like, such as sulfite as sodium sulfite, potassium sulfite, and thelike, and such a bromide as sodium bromide, potassium bromide, ammoniumbromide, and the like. Further, the solution may, if necessary, containany of known development restrainers, a thiocyanate such as sodiumthiocyanate; potassium thiocyanate, ammonium thiocyanate, and the like;a chloride such as ammonium chloride, potassium chloride, sodiumchloride, and the like; an organic solvent such as ethylene glycol,diethylene glycol, methanol, ethanol, n-butanol, benzyl alcohol,acetone, dimethylformamide, and the like; an amine such ashydroxylamine, ethanolamine, ethylenediamine, diethanolamine, and thelike; a water softener such as sodium hexametaphosphate, sodiumtripolyphosphate, ethylenediamine tetraacetate, diethylenetriaminepentaacetate, and the like; and a water-soluble brightening agent, andthe like.

The color developing solution or activator solution used in the presentinvention may contain an auxiliary developing agent. As the auxiliarydeveloping agent, 1-aryl-3-pyrazolidone derivatives are preferably used,any of which is used in an amount of from 1 mg to 1 g, and preferablyfrom 10 mg to 500 mg per liter of the color developing or activatorsolution. Typical examples of such auxiliary developing agents are1-phenyl-3-pyrazolidone, 4-methyl-1-phenyl-3-pyrazolidone,4,4-dimethyl-1-phenyl-3-pyrazolidone,4-methyl-4-hydroxymethyl-1-phenyl-3-pyrazolidone,4-methyl-4-hydroxymethyl-1-(p-tolyl)-3-pyrazolidone, and the like.

The color developing solution or activator solution used in theinvention is kept alkaline in the usual way, the hydrogen ionconcentration of which, although arbitrarily selectable according to thekind, composition, purposes and uses of the negative material of theprint-making light-sensitive material used, is generally from pH 9.5 topH 13.5.

The color developing solution or activator solution used in thisinvention is generally used in a certain temperature range. Thetemperature range, although arbitrarily selectable according to thekind, composition, uses and purposes of the print-making light-sensitivematerial of the invention, is preferably from 15° C. to 70° C., and morepreferably from 30° C. to 50° C.

As the bleaching agent for use in the bleaching bath or in thebleach-fixing bath, any known compounds may be used which includeaminopolycarboxylic acid ferric complex salts such as ferric-sodiumethylenediamine tetraacetate, ferric-ammonium ethylenediaminetetraacetate, and the like, and persulfates such as ammonium persulfate,sodium persulfate, and the like.

As the fixing agent for use in the fixing bath or in the bleach-fixingbath, any known compounds may be used which include thiosulfates such assodium thiosulfate, ammonium thiosulfate, and the like, water-solublesulfur-containing diols such as 3,6-dithio-1,8-octanediol,3,6,9,12-tetrathio-1,14-tetradecanediol, and the like, and water-solublesulfur-containing dibasic acid such as ethylene-bis-thioglycolic acid,sodium ethylene-bis-thioglycolate, and the like.

EFFECTS OF THE INVENTION

According to the present invention, the deterioration (sweat phenomenon)of the surface gloss of the light-sensitive material caused with timeafter the development of the material by heat, light, moisture, and thelike, is remarkably reduced; particularly the deterioration of thesurface gloss by light is significantly reduced.

And the resistance to light of the color-developed dye image becomesmarkedly excellent, so that very little discoloration occurs. The colorbalance of the dye image, even when discolored, is sufficientlyretained.

Further, very few static marks are produced when coating the componentlayers and when transporting the light-sensitive material through theinside of a photographic printer.

EXAMPLES OF THE INVENTION

The present invention will be illustrated further in detail by thefollowing examples.

EXAMPLE 1

A light-sensitive material was prepared having the component layers asgiven in Table 1.

TABLE 1 Coated Coated amt. Coated amt. of UV of Ag amt. of absorbingLayer (mg/ gelatin agent Coup- No. Layer dm²) (mg/dm²) (mg/dm²) lerLayer 6 Protective — 15 0 or 4.0 — layer Layer 5 Red- 3.0 20 — (C-1)sensitive *EM layer Layer 4 2nd — 15 UV-7S 4.0 — interlayer Layer 3Green- 3.0 20 — (M-1) sensitive EM layer Layer 2 1st — 15 — — interlayerLayer 1 Blue- 4.0 20 — (Y-1) sensitive EM layer Polyethylene-coatedpaper support *EM represents “emulsion”

The kind of the ultraviolet absorbing agent and the kind and amount ofthe high-boiling organic solvent used in the protective layer and thesecond interlayer were varied as shown in Table 2, thereby preparingnine samples.

In addition, the structures of the used yellow coupler Y-1, magentacoupler M-1 and cyan coupler C-1 are as indicated below. And in Table 2,the “DBP” represents dibutyl phthalate and the “DOP” represents dioctylphthalate.

TABLE 2 High-boiling organic solvent Proportional Sam- amt. to UV ple UVabsorbing agent absorbing No. in protective layer Kind agent Remarks 1 —— — Control 2 (UV-7S) DBP 1 ″ 3 (UV-7S):(UV-4S) = 1:1 ″ 1 ″ 4 (UV-2L)DOP 1 Invention 5 ″ ″ 0.5 ″ 6 ″ — 0 ″ 7 (UV-12L) DOP 0.5 ″ 8(UV-12L):(UV-7S) = 1:1 ″ 0.5 ″ 9 ″ — 0 ″

Each of the thus prepared samples remaining unexposed was processedaccording to the following processes, whereby a plain (non-imagewise)sample was obtained.

Processing steps Processing time Processing temp. Color development 3.5minutes 33° C. Bleach-fixing 1.5 minutes 33° C. Washing   3 minutes 33°C. Drying — 80° C.

Color developer bath composition: Pure water 700 ml Benzyl alcohol 15 mlDiethylene glycol 15 ml Hydroxylamine sulfate 2 gN-ethyl-N-β-methanesulfonamidoethyl- 4.4 g 3-methyl-4-aminoanilinesulfate Potassium carbonate 30 g Potassium bromide 0.4 g Potassiumchloride 0.5 g Potassium sulfite 2 g Pure water to make 1 liter (pH =10.2) Bleach-fixing bath composition: Iron-ammonium ethylenediamine- 61g tetraacetate Diammonium ethylenediamine- 5 g tetraacetate Ammoniumthiosulfate 125 g Sodium metabisulfate 13 g Sodium sulfite 2.7 g Waterto make 1 liter (pH = 7.2)

The thus obtained plain white samples were subjected to surface glossdeterioration tests under the following various aging conditions.Surface gloss measurements were made by use of a glossmeter manufacturedby Tokyo Denshoku K. K. The results obtained by measuring the samplesimmediately after the processing and the samples after the aging testsare as indicated in Table 3.

Aging conditions A: 77° C. without humidification 14 days B: 70° C. 80%Relative humidity 14 days C: Xenon fademeter 400 hours

TABLE 3 Surface gloss (%) A 77° C. without B C Right after humidifi- 70°C. Xenon Sample No. processing cation 80% RH fademeter 1 Control 94 8785 83 2 Control 81 78 72 51 3 Control 83 80 75 54 4 Invention 88 84 8075 5 Invention 90 85 81 78 6 Invnetion 92 86 83 80 7 Invention 91 85 8278 8 Invention 89 84 81 77 9 Invention 90 85 82 79

It is apparent from Table 3 that samples No. 2 and No. 3 which containin the protective layers thereof ultraviolet absorbing agents for thepurpose of improving the resistance to light of the dyes to be formedshow remarkable deterioration of the surface gloss thereof by light,heat and moisture, whereas samples No. 4 to No. 9 for the presentinvention show no deterioration and are much improved in this respect.

Next, these nine samples were subjected to light resistance tests underthe testing conditions comprising the above condition C and exposure tothe direct rays of the sun over a period of 30 days.

The samples which were used in the test are those prepared in the mannerthat the samples each was exposed through an optical step wedge to ablue light, green light and red light by use of a sensitometer (ModelKS-7, manufactured by Konishiroku Photo Ind. Co., Ltd.) and thenprocessed in the foregoing development processes, whereby three color(yellow, magenta and cyan) separation samples were obtained. As ameasure of the resistance to light, the dye residual degree was usedwhich is expressed by the percentage of the reflection density after theexposure to the reflection density (1.0) before the exposure.

In the measurement, as to those whose plain white area is changed toyellow by the exposure (particularly in the yellow-color-developedsamples) to affect the density measurement, the remainder of themeasured density from which the yellow-discolored density is subtractedwas regarded as the after-exposure density. For instance, when thereadings were adjusted so that the before-exposure plain white densityis 0.00 and the before-exposure yellow density is 1.00, if theafter-exposure densities of the plain white area is 0.18 and of theyellow dye is 0.78, then the dye residual percentage is(0.78−0.18)/1.00×100=60%. The results are as shown in Table 4.

TABLE 4 Xenon fademeter Sunlight (direct rays) 400 hrs. 30 days SampleNo. Yellow Magenta Cyan Yellow Magenta Cyan 1 Control 34 32 30 41 38 352 Control 52 49 65 61 54 74 3 Control 54 51 66 62 57 75 4 Invention 5859 67 66 71 75 5 Invention 57 58 67 66 70 74 6 Invnetion 58 58 66 66 7175 7 Invention 60 61 68 68 73 77 8 Invention 59 60 67 67 72 76 9Invention 59 61 67 68 72 77

From the results shown in Table 4 it is apparent that samples No. 4 toNo. 9, as compared to samples No. 2 and No. 3, are much improved on theresistance to light of the yellow, magenta and cyan dyes thereof,particularly the improvement on the light resistance of the magenta dyeis significant.

EXAMPLE 2

A light-sensitive material was prepared having the component layers asshown in Table 5.

TABLE 5 Coated Coated amt. Coated amt. of UV of Ag amt. of absorbingLayer (mg/ gelatin agent Coup- No. Layer dm²) (mg/dm²) (mg/dm²) lerLayer 7 Protective — 10 — — layer Layer 6 3rd — 10 4.0 — interlayerLayer 5 Red- 3.0 20 — C-2 sensitive EM layer Layer 4 2nd — 15 4.0 —interlayer Layer 3 Green- 3.0 20 — M-2 sensitive EM layer Layer 2 1st —15 — — interlayer Layer 1 Blue- 4.0 20 — Y-2 sensitive EM layerPolyethylene-coated paper support

The structures of the used couplers Y-2, M-2 and C-2 are as shown below.And in the second layer the UV-7S and UV-4S were used in the proportionof 1:1.

In the above layer composition, the kind of the ultraviolet absorbingagent and the kind and amount of the high-boiling organic solvent usedin the third interlayer were varied as given in Table 6, whereby samplesNo. 1 to No. 5 were prepared.

TABLE 6 High-boiling organic solvent Sam- Proportional ple UV absorbingagent amt. to UV No. in 3rd interlayer Kind absorbing agent Remarks 1(UV-7S) DBP 1 Control 2 (UV-4S) DOP 1 ″ 3 (UV-1L) DBP 0.5 Invention 4(UV-3L) DOP 0 ″ 5 (UV-3L):(UV-7S) = 1:1 DOP 0.5 ″

The thus prepared five samples were tested in the same manner as inExample 1.

The results of the surface gloss test are as shown in Table 7 and theresults of the light resistance test are as in Table 8.

TABLE 7 Surface gloss (%) A 77° C. without B C Right after humidifi- 70°C. Xenon Sample No. processing cation 80% RH fademeter 1 Control 88 8481 78 2 Control 87 85 80 75 3 Invention 94 92 90 90 4 Invention 95 93 9190 5 Invention 94 91 89 88

TABLE 8 Fluorescent light Sunlight (under glass) tester 400 hrs. 45 daysSample No. Yellow Magenta Cyan Yellow Magenta Cyan 1 Control 64 61 73 5757 75 2 Control 63 62 72 58 58 75 3 Control 66 67 75 61 63 77 4Invention 65 68 74 60 64 77 5 Invention 67 69 76 61 64 78

From the results shown in Table 7 and Table 8 it is apparent that in thesamples for the present invention, not only the formed dyes are highlyresistant against light but also the surface gloss is remarkablyimproved.

What is claimed is:
 1. A color photographic light-sensitive material comprising a reflective support having thereon a plurality of silver halide emulsion layers of which the emulsion layer located farthest from said support has, on each of both the support side thereof and the uppermost side at least one nonlight-sensitive layer containing an effective amount of an ultraviolet absorbing agent, said ultraviolet absorbing agent being used in said nonlight-sensitive layer on the uppermost side of said emulsion layer being a 2-(2′-hydroxyphenyl)benzotriazole-type compound which is in the liquid form at normal room temperature, and wherein said 2-(2′-hydroxyphenyl)benzotriazole-type compound is selected from the group consisting of has the following formula:

wherein R₁ and R₂ independently represent an alkyl, an aryl, an alkoxy and an aryloxy radical, and R₃ represents a hydrogen atom, a halogen atom, an alkyl, an aryl, an alkoxy, an aryloxy, an alkenyl, a nitro or hydroxy radical;

wherein R₄ represents a methyl, ethyl or propyl radical, R₅ represents a secondary alkyl having from 4 to 10 carbon atoms, R₆ represents a hydrogen atom, a halogen atom, an alkyl, or an alkoxy radical having from 1 to 8 carbon atoms;

wherein R₇, R₈ and R₉ independently represent an alkyl radical having from 4 to 10 carbon atoms, provided that at least one of R₇, R₈ and R₉ represents a secondary alkyl;

wherein R₁₀ represents a secondary or tertiary alkyl having from 1 to 8 carbon atoms, X represents an alkylene having from 1 to 6 carbon atoms, R₁₁ represents an alkyl group having from 1 to 12 carbon atoms, R₁₂ represents a hydrogen atom, a halogen atom, an alkyl or an alkoxy radical having from 1 to 8 carbon atoms; and

wherein R₁₃ and R₁₄ independently represent a secondary alkyl having from 4 to 10 carbon atoms and R₁₅ represents a hydrogen atom, a halogen atom and an alkoxy radical having from 1 to 8 carbon atoms. .
 2. A material according to claim 1, wherein said plurality of silver halide emulsion layers are a yellow coupler-containing emulsion layer, a magenta coupler-containing emulsion layer and a cyan coupler-containing emulsion layer.
 3. A material according to claim 1, wherein said emulsion layer located farthest from said support is a cyan coupler-containing layer.
 4. A material according to claim 2, wherein said yellow coupler-containing emulsion layer, said magenta coupler-containing emulsion layer and said cyan coupler-containing emulsion layer are provided on said support in this order.
 5. A material according to claim 2, wherein said yellow coupler-containing emulsion layer is a blue-light-sensitive emulsion layer, said magenta coupler-containing emulsion layer is a green-light-sensitive emulsion layer and said cyan coupler-containing emulsion layer is a red-light-sensitive emulsion layer.
 6. A material according to claim 1, wherein said benzotriazole-type compound has the melting point of not higher than 30° C.
 7. A material according to claim 1, wherein said benzotriazole-type compound has the melting point of not higher than 15° C.
 8. A color photographic light-sensitive material comprising a reflective support having thereon a plurality of silver halide emulsion layers in which the emulsion layer located farthest from said support has, on each of both the support side thereof and the side opposite from said support, at least one nonlight-sensitive layer containing an effective amount of an ultraviolet absorbing agent, said ultraviolet absorbing agent in said nonlight-sensitive layer on the side of said emulsion layer opposite from said support comprising a 2 -( 2′-hydroxyphenyl)benzotriazole-type compound which is in the liquid form at normal room temperature, and wherein said 2 -( 2′-hydroxyphenyl)benzotriazole-type compound has the formula

wherein R ₄ represents a methyl, ethyl or propyl radical, R ₅ represents a secondary alkyl having from 4 to 10 carbon atoms, and R ₆ represents a hydrogen atom, halogen atom, an alkyl, or an alkoxy radical having from 1 to 8 carbon atoms.
 9. A material according to claim 8, wherein said plurality of silver halide emulsion layers are a yellow coupler-containing emulsion layer, a magenta coupler-containing emulsion layer and a cyan coupler-containing emulsion layer.
 10. A material according to claim 8, wherein said emulsion layer located farthest from said support is a cyan coupler-containing layer.
 11. A material according to claim 9, wherein said yellow coupler-containing emulsion layer, said magenta coupler-containing emulsion layer and said cyan coupler-containing emulsion layer are provided on said support in this order.
 12. A material according to claim 9, wherein said yellow coupler-containing emulsion layer is a blue-light-sensitive emulsion layer, said magenta coupler-containing emulsion layer is a green-light-sensitive emulsion layer and said cyan coupler-containing emulsion layer is a red-light-sensitive emulsion layer.
 13. A material according to claim 8, wherein said benzotriazole-type compound has a melting point of not higher than 30° C.
 14. A material according to claim 8, wherein said benzotriazole-type compound has a melting point of not higher than 15° C.
 15. A color photographic light-sensitive material comprising a reflective support having thereon a plurality of silver halide emulsion layers in which the emulsion layer located farthest from said support has, on each of both the support side thereof and the side opposite from said support, at least one nonlight-sensitive layer containing an effective amount of an ultraviolet absorbing agent, said ultraviolet absorbing agent in said nonlight-sensitive layer on the side of said emulsion layer opposite from said support comprising a 2 -( 2′-hydroxyphenyl)benzotriazole-type compound which is in the liquid form at normal room temperature, and wherein said 2 -( 2′-hydroxyphenyl)benzotriazole-type compound has the formula

wherein R ₇ , R ₈ and R ₉ independently represent an alkyl radical having from 4 to 10 carbon atoms, provided that at least one of R ₇ , R ₈ and R ₉ represents a secondary alkyl.
 16. A material according to claim 15, wherein said plurality of silver halide emulsion layers are a yellow coupler-containing emulsion layer, a magenta coupler-containing emulsion layer and a cyan coupler-containing emulsion layer.
 17. A material according to claim 15, wherein said emulsion layer located farthest from said support is a cyan coupler-containing layer.
 18. A material according to claim 16, wherein said yellow coupler-containing emulsion layer, said magenta coupler-containing emulsion layer and said cyan coupler-containing emulsion layer are provided on said support in this order.
 19. A material according to claim 16, wherein said yellow coupler-containing emulsion layer is a blue-light-sensitive emulsion layer, said magenta coupler-containing emulsion layer is a green-light sensitive emulsion layer and said cyan coupler-containing emulsion layer is a red-light-sensitive emulsion layer.
 20. A material according to claim 15, wherein said benzotriazole-type compound has a melting point of not higher than 30° C.
 21. A material according to claim 15, wherein said benzotriazole-type compound has a melting point of not higher than 15° C.
 22. A color photographic light-sensitive material comprising a reflective support having thereon a plurality of silver halide emulsion layers in which the emulsion layer located farthest from said support has, on each of both the support side thereof and the side opposite from said support, at least one nonlight-sensitive layer containing an effective amount of an ultraviolet absorbing agent, said ultraviolet absorbing agent in said nonlight-sensitive layer on the side of said emulsion layer opposite from said support comprising a 2 -( 2′-hydroxyphenyl)benzotriazole-type compound which is in the liquid form at normal room temperature, and wherein said 2 -( 2′-hydroxyphenyl)benzotriazole-type compound has the formula

wherein R ₁₀ represents a secondary or tertiary alkyl having from 3 to 8 carbon atoms, X represents an alkylene having from 1 to 6 carbon atoms, R ₁₁ represents an alkyl group having from 1 to 12 carbon atoms, and R ₁₂ represents a hydrogen atom, a halogen atom, an alkyl or an alkoxy radical having from 1 to 8 carbon atoms.
 23. A material according to claim 22, wherein said plurality of silver halide emulsion layers are a yellow coupler-containing emulsion layer, a magenta coupler-containing emulsion layer and a cyan coupler-containing emulsion layer.
 24. A material according to claim 22, wherein said emulsion layer located farthest from said support is a cyan coupler-containing layer.
 25. A material according to claim 23, wherein said yellow coupler-containing emulsion layer, said magenta coupler-containing emulsion layer and said cyan coupler-containing emulsion layer are provided on said support in this order.
 26. A material according to claim 23, wherein said yellow coupler-containing emulsion layer is a blue-light-sensitive emulsion layer, said magenta coupler-containing emulsion layer is a green-light-sensitive emulsion layer and said cyan coupler-containing emulsion layer is a red-light-emulsion layer.
 27. A material according to claim 22, wherein said benzotriazole-type compound has a melting point of not higher than 30° C.
 28. A material according to claim 22, wherein said benzotriazole-type compound has a melting point of not higher than 15° C.
 29. A color photographic light-sensitive material comprising a reflective support having thereon a plurality of silver halide emulsion layers in which the emulsion layer located farthest from said support has, on each of both the support side thereof and the side opposite from said support, at least one nonlight-sensitive layer containing an effective amount of an ultraviolet absorbing agent, said ultraviolet absorbing agent in said nonlight-sensitive layer on the side of said emulsion layer opposite from said support comprising a 2 -( 2′-hydroxyphenyl)benzotriazole-type compound which is in the liquid form at normal room temperature, and wherein said 2 -( 2′-hydroxyphenyl)benzotriazole-type compound has the formula

wherein R ₁₃ and R ₁₄ independently represent a secondary alkyl having from 4 to 10 carbon atoms and R ₁₅ represents a hydrogen atom, a halogen atom, an alkyl, or an alkoxy radical having from 1 to 8 carbon atoms.
 30. A material according to claim 29, wherein said plurality of silver halide emulsion layers are a yellow coupler-containing emulsion layer, a magenta coupler-containing emulsion layer and a cyan coupler-containing emulsion layer.
 31. A material according to claim 29, wherein said emulsion layer located farthest from said support is a cyan coupler-containing layer.
 32. A material according to claim 30, wherein said yellow coupler-containing emulsion layer, said magenta coupler-containing emulsion layer and said cyan coupler-containing emulsion layer are provided on said support in this order.
 33. A material according to claim 30, wherein said yellow coupler-containing emulsion layer is a blue-light-sensitive emulsion layer, said magenta coupler-containing emulsion layer is a green-light-sensitive emulsion layer and said cyan coupler-containing emulsion layer is a red-light-sensitive emulsion layer.
 34. A material according to claim 29, wherein said benzotriazole-type compound has a melting point of not higher than 30° C.
 35. A material according to claim 29, wherein said benzotriazole-type compound has a melting point of not higher than 15° C. 